Integrated Electrochemical Processes for CO2 Capture

and Conversion to Commodity Chemicals

Project Number: DE-FE0004271

Dr. Jie Wu,1,2 Dr. Jennifer A. Kozak,1,2 Xiao Su,2 Dr. Fritz Simeon,2 Prof. Timothy F. Jamison*,1 and Prof. T. Alan Hatton,*,2

1Department of Chemistry and 2Department of Chemical Engineering Massachusetts Institute of Technology

U.S. Department of Energy National Energy Technology Laboratory

Carbon Storage R&D Project Review Meeting Developing the Technologies and

Infrastructure for CCS August 20-22, 2013

2

Presentation Outline

• Motivation, Goals, Objectives • Background • Cyclic Carbonate Synthesis via Catalytic

Coupling of CO2 and Epoxides • Cyclic Carbonate Synthesis via oxidative

carboxylation using CO2 and Olefins • Conclusions

3

Benefit to the Program

• Identify the Program goals being addressed. – Develop technologies to demonstrate that 99 percent

of injected CO2 remains in the injection zones. • The research project is developing a novel approach to

capturing and converting CO2 into commodity chemicals, which may thus reduce the burden on CO2 storage sites, in addition to providing a means to reduce anthropogenic CO2 emissions and an inexpensive method for producing useful materials from CO2.

4

Project Overview: Goals and Objectives

• To develop and demonstrate a novel chemical sequestration technology that utilizes CO2 from dilute gas streams generated at industrial carbon emitters as a raw material in order to produce useful commodity chemicals. – Single electrochemical system for CO2 capture and

chemical conversion – Coupled system for CO2 capture and chemical

conversion

5

Project Overview: Goals and Objectives

• To develop and demonstrate a novel chemical sequestration technology that utilizes CO2 from dilute gas streams generated at industrial carbon emitters as a raw material in order to produce useful commodity chemicals. – Single electrochemical system for CO2 capture and

chemical conversion – Coupled system for CO2 capture and chemical

conversion

6

Technical Status

Accomplishments to Date – A novel catalytic method for the continuous chemical

conversion of CO2 has been developed and thoroughly investigated mechanistically.

– A mechanism-guided design of sequential continuous flow systems has been developed to achieve a variety of carbonates using CO2 and olefins.

• Detailed mechanistic exploration. • Several advantages over existing methods. • Springboard for development of several other classes of CO2

conversion.

7

8

Motivation for CO2 Capture, Sequestration, and Conversion

• Anthropogenic carbon dioxide (CO2) • considered a primary cause of global

climate change • coal-fired power plants, and the petroleum

and natural gas industries account for 86% of anthropogenic CO2

• we will continue to depend on non-renewable fossil fuels for the next several decades

• The CO2 cycle is not balanced • 3.9% excess (caused by anthropogenic

CO2) with respect to the yearly CO2-flow in the natural “carbon cycle”

• Only 30-35% of the chemical energy content associated with anthropogenic CO2 emissions is converted into various forms of energy.

• 65-75% is lost as heat to the Earth’s atmosphere.

http://www.telegraph.co.uk/earth/earthnews/5257162/Power-plants-could-store-carbon-dioxide-under-North-Sea.html

9

Carbon Dioxide as a Chemical Feedstock

Arakawa, H.; Aresta, M.; Armor, J. N.; Barteau, M. A.; Beckman, E. J.; Bell, A. T.; Bercaw, J. E.; Creutz, C.; Dinjus, E.; Dixon, D. A.; Domen, K.; DuBois, D. L.; Eckert, J.; Fujita, E.; Gibson, D. H.; Goddard, W. A.; Goodman, D. W.; Keller, J.; Kubas, G. J.; Kung, H. H.; Lyons, J. E.; Manzer, L. E.; Marks, T. J.*; Morokuma, K.; Nicholas, K. M.; Periana, R.; Que, L.; Rostrup-Nielson, J.; Sachtler, W. M. H.; Schmidt, L. D.; Sen, A.; Somorjai, G. A.; Stair, P. C.; Stults, B. R.; Tumas, W. Chem. Rev. 2001, 101, 953.

• What is the motivation for producing chemicals from CO2?

• CO2 is an inexpensive, non-flammable, non-toxic feedstock that is stable, easy to store, and readily available.

• It can be used to replace toxic chemicals such as phosgene and isocyanates. • CO2 is a renewable resource, as compared to oil or coal; the future supply of

fossil fuels is considered limited. • The use of CO2 in new routes to existing chemical intermediates and

products could be more efficient and economical than current technologies. • The production of chemicals from CO2 could have a small but likely significant

positive impact on the global carbon balance. • CO2 is an exceptionally inexpensive source of carbon, at ~0.1 ¢/mol. • For comparison: Ethylene, ~3 ¢/mol (1.5 ¢/mol of C atoms); propylene, (~5

¢/mol, 1.5 ¢/mol of C atoms).

Gas/Liquid Continuous Flow Chemistry

Traditional batch reactions: Continuous flow synthesis:

• Exceedingly high surface-to-volume ratio

• Efficient heterogeneous mass-transfer

• Excellent reproducibility

• Reduced equipment footprint and labor work

• Low interaction and mass transfer

• Interfacial area of ca. 100-300 m2/m3

liq

• High capital and infrastructure costs

• Associated safety factors

Conversion of CO2 Using Epoxides

Bromine-catalyzed conversion of CO2 and epoxides to cyclic carbonates:

O O

O

R

• polar aprotic solvents • electrolytes in lithium ion batteries • constituents in oils and paints • antifoam agents for antifreeze and plasticizers • raw materials for the synthesis of polycarbonates and

polyurethanes

O

5

5 mol %

CO2, DMF, 120 oC

O O

O

5

Batch Results (6 h):75 % yield

N Br

O

O

Ph

O

OO Ph

O

5 mol % Flow Results (30 min):90-98 % yield

Kozak, J. A.; Wu, J.; Su, X.; Simeon, F.; Hatton, T. A.; Jamison, T. F., “Bromine-Catalyzed Conversion of CO2 and Epoxides to Cyclic Carbonates under Continuous Flow Conditions,” 2013 (submitted for publication).

(benzoyl peroxide = BPO)

Schematic of the Continuous Reactor

12

2 mL stainless-steel reactor

120 °C

Epoxide + Solvent

Stream 2: Liquid

CO2mass flowcontroller trap

pressuregaugeStream 1: Gas

6-wayvalve

sample loop

bomb (bulkcollection)

samplecollectionsyringe

(EtOAc)

N2

slowbleed

one-wayvalve

Slug flow reduces dispersion; provides efficient mass transfer contact Well-controlled conditions for evaluation of reaction kinetics and mechanisms

Kinetic Study

Proposed Mechanism Based on Kinetics Investigations

14

+ Br

N

O

O

+ H N

OCH3

CH3

H2CN

H3C

2 Br Br2

with or without BPONBr

O

O

(twice)

H +

N

O

O

+ H N

O

H3CN

O

O

H2CN

H3C

O

O

H

NHS

N

O

O O

R

OO

O

R

Br2

CO2

+

+

+ Br2

O

R

Br

+ Brcat. DMF

O

R

Br

+

+ Br +

H N

OCH3

CH3

NMe

Me H

OO

O

NMe

Me H

OO

O

H N

OCH3

CH3

OR

OBr

O

O

H

NMe

Me

OR

OBr

O

O

H

NMe

Me

Capture of CO2 Using Simple Olefins

Originally designed multi-stream f low

O O

O

RR

NBS, DBUDMF, H2O

CO2 • Low reaction rate (especially f or aliphatic olef ins)• Reagent incompatibility ( such as DBU and NBS)

Mechanism-guided design of f low

O O

O

R

RNBS, acetone

NH4OAc H2O

• Signif icantly enhanced rate• Minimized by-products• High yield• Wide substrate scope

• •

CO2

DBU

mechanistic investigation

Mechanism-guided flow design to avoid reagent incompatibility:

Low solubility of olefins in DMF/H2O Interaction between NBS and DBU (DBU = 1,8-diazabicycloundec-7-ene) Dibromide formation promoted by DBU; form bromohydrins before addition of DBU

Ph

OO

O

Ph PhBr

Ph

OHBr

DBU CO2

Ph

OBr

Ph

O

O OH

O

Ph

OBr

O

OH

B

A path a

path c

path b

path d

PhPh

OO

ONBS (1 equiv), DBU (1.6 equiv)

3 h, Parr reactor

65%

+Ph

Br

20%92% conversion

Br

DBU

H2O

H2O (1.5 M), CO2 (300 psi)

C

D

B

NBS

C

N

NH

HCO3

Ph

OBr

O

OH

•N

N

N

O

OD

•

Br

Possible Reaction Pathways

Bromohydroxylation pathway

DBU activated CO2

water induced bicarbonate anion Bromohydrin generated from olefins and NBS in water.

• Water was necessary • DBU significantly decreased the rxn rate (indicated formation of DBU-NBS complex) • CO2 increased the reaction rate (indicated DBU-CO2 complex formation) • DMF helped formation of epoxide.

NBS (1 equiv)DBU (1.6 equiv)CO2 (dry ice, 5 equiv)60 oC, 3 h (sealed tubes)

Nap

OO

O+

Nap

OHBr Nap

O+

A C D

+Nap

BrBr

B

entry condition conversiona yield of Aa other productsa

1 100% 0% 87% CNBS +H2O

2 26% 0% 15% DNBS+H2O+DBU

3 84% 55% 8% DNBS+H2O+DBU+CO2

4 50% 0% 45% BNBS+DMF+DBU+CO2

a Conversion and yield are based on analysis of crude 1H NMR spectra using trichloroethylene as the external standard.

Mechanistic Study

packed-bedreactor

reagents

Stream 2: Liquid

CO2mass flowcontroller

pressuregaugeStream 1: Gas

6-wayvalve

sample loop

bomb (bulkcollection)

samplecollectionsyringe

(EtOAc)

N2

slowbleed

R

NBS (1.2 equiv), DBU (1 equiv),CO2 (130 psi), Vg/Vl = 1:1,

R

OO

ODMF/H2O (2:1, 0.4 M)

100 oC, 7.5 min

Packed-bed flow reactor

Ph : 100% conversion 85% yield

: 15% conversion 10% yield

PhO

Initial Two-Stream Gas/Liquid Flow Setup

NBS (1.2 eq)acetone

30 min, 40 oC

RCO2 (130 psi)

H2O + DBU(1.3 eq)

10 min, 100 oC

RO

OO

NH4OAc (0.1 eq)H2O

Sequential Transformations in Flow

Me OPhO

OO

75%

OO

O

43%

MeO OO

O

O82%

NC OO

O

71%5

PhMe2SiO

OO

79%

Me OO

O

O85%

HOO

OO

73%

O

O O

89%

O

O O

OO

O

49%

OO

O

EtEt

87%

OO

O

MeEt

85%

PhO

OO

80%

OO

O

85%

N

OO

O

48%

OO

O

S

N Me62% 52%

OO

O

OO

O

Cl MeO

85% 66%

OO

O

88%CF3

OO

O

72%

O

O

OO

O

72%

CO2 tank N2 tank

slow bleed

reactor

syringe pump

asia pump mass flow controller

collection bomb

Sequential Flow Setup

NBS (1.2 equiv)NH4OAc (0.1 equiv)

acetone/H2O (2:1)

CO2 (250 psi)

HO

Parr reactor100 oC, 30 min

HO

HO

OO

O

O

15%

45%

DBU (2.5 equiv), H2O

NBS (1.2 equiv)NH4OAc (0.1 equiv)

acetone/H2O (2:1)

CO2 (120 psi)

40 oC, 30 min100 oC, 10 min HO

OO

O

73%

DBU (2.5 equiv), H2O

100 % conversion

100 % conversion

batch

f low

+40 oC, 30 min

no epoxide products

Comparison of sequential transformations between batch and flow:

Sequential Transformation in Flow

CO2 tank mass flowcontroller

pressuregauge

NBS + olefin + acetone

6-wayvalve

sample loop

bomb

samplecollectionsyringe

(EtOAc)

N2slowbleed

1.2 mLpacked-bed

reactorRt=10 min0.9 mL

PFA tubing, Rt = 30 min

DBU+H2O

TEFZEL tubing

feature function

• excellent surface-to-volume ratio • increases the reaction rate; suppresses byproduct formation

• no headspace • reduced equipment footprint (safety)

• acetone as co-solvent • avoids phase-transfer-reagents

• elevated temperature and pressure • provides rate enhancement

• packed-bed reactor • increases the reaction rate; more steady flow

• sequential reactions • significantly enhances the reaction rate; avoids reagent incompatibility

NH4OAc + H2O

stainless-steelT-mixer

Sequential Transformation in Flow

An Integrated Capture and Conversion System

Loaded Sorbent

Anode (+)

Cathode (-)

Lean Gas

Feed Gas

Flash Tank

Act

ivat

ed S

orbe

nt

Absorption Column

Electrochemical Regeneration

Capture

High pressure CO2 stream

Continuous Flow CO2 Conversion Unit

Reagent

Products

Carbon Conversion Unit

Carbon Capture Unit “Electrochemically-Mediated

Amine Regeneration”

O

O O

O

Organocatalytic Route - with decoupled capture and conversion units

Temperature (oC)

Ano

de P

ress

ure

(Bar

)

Efficiency

50 60 70 802

6

10

14

18

0.45

0.5

0.55

0.6

0.65

Absorber

Syringe Pump

EMAR Pump

Power Supply

Gas/Liquid Separator

Heated Water Bath

Coil Reactor

EMAR Cell

Summary

– Key Findings • A novel mechanism of epoxide activation was

discovered, and its impact may be very broad. • A sequential flow system works best for the

conversion of CO2 using olefins due to the incompatibility between DBU and NBS.

– Lessons Learned • Continuous processing is superior to batch for

elucidation of conversion mechanisms and kinetics

25

Acknowledgments – MIT

• Dr. Jie Wu • Dr. Jennifer A. Kozak • Xiao Su • Dr. Fritz Simeon • Prof. Timothy F. Jamison • Prof. T. Alan Hatton

– Siemens (Life Cycle Analyses)

• Dr. Elena Arvinitis • Dr. Noorie Rajvanshi • Dr. Amit Kapur

– DOE-NETL

• Dr. Bill O’Dowd 26

Appendix – These slides will not be discussed during the

presentation, but are mandatory

27

28

Gantt Chart

29

Organization Chart

Department of Energy

Project Management: Prof. T. Alan Hatton (MIT)

(Technical Point of Contact)

Technology Development: Prof. T. Alan Hatton (MIT)

Prof. Timothy F. Jamison (MIT)

Team Members: Dr. Fritz Simeon (MIT)

Dr. Jennifer A. Kozak (MIT) Dr. Jie Wu (MIT)

Su Xiao (MIT)

Life Cycle Assessments: Dr. Elena Arvanitis (Siemens)

Dr. Noorie Rajvanshi (Siemens) Dr. Amit Kapur (Siemens)

30

Gantt Chart Sub-Task

Project Milestone Description

Project Duration:10/01/2010-09/30/2013 Planned

Start Date:

Planned End

Date:

Actual Start Date:

Actual End

Date: Comments Project Year 1 Project Year

2 Project Year 3

1 2 3 4 5 6 7 8 9 10 11 12

1.1 Project management plan ✔ 10/01/10 12/31/12 10/01/10

1.2 Project management ✔ ✔ ✔ ✔ ✔ ✔ ✔ ✔ ✔ ✔ ✔ 10/01/10 12/31/12 10/01/10 12/31/12 Submission of Q1 progress report

2.1 Chemical reaction between bis(carbonate)s and electrophiles

✔ ✔ 10/01/10 03/31/11 10/01/10 03/31/11

2.2 Molecular characterization of “intermediate” complex ✔ ✔ 10/01/10 03/31/11 10/01/10 03/31/11

2.3 Reaction kinetic analysis of “intermediate” complex formation

✔ ✔ 04/01/11 09/30/11 04/01/11 09/30/11

2.4 Electrochemistry of “intermediate” complex formation

✔ ✔ 04/01/11 09/30/11 04/01/11 09/30/11

2.5 Chemical sequestration with various redox-active molecules

✔ ✔ 04/01/11 09/30/11 04/01/11 09/30/11

2.6 Organocatalytic chemical sequestration of CO2 ✔ ✔ ✔ ✔ 10/01/11 09/30/12 10/01/11 09/30/12

Investigation of organocatalyst (NBS system) for production of cyclic carbonate from cyclic oxide and CO2

2.7 Reaction kinetic analysis of organocatalytic route for CO2 conversion

✔ ✔ ✔ ✔ 10/01/11 09/30/12 10/01/11 09/30/12

Reaction kinetic of organocatalytic process (NBS system) for cyclic carbonate production from cyclic oxide and CO2

2.8 Organocatalyst for continuous chemical sequestration of CO2

✔ ✔ ✔ ✔ 10/01/11 12/31/12 10/01/11 12/31/12

Investigation of organocatalyst (NBS system) for production of cyclic carbonate from cyclic oxide and CO2 with continuous flow reactor

3.1 Chemical analysis of integrated chemical sequestration

✔ ✔ ✔ ✔ ✔ 01/01/11 09/30/12 01/01/11 09/30/12

Investigation of “active” catalyst in organocatalytic process for cyclic carbonate production from cyclic oxide and CO2

3.2 Chemical sequestration prototype unit ✔ ✔ 04/01/12 09/30/12 04/01/12 09/30/12 Development of continuous flow

reactor.

4.1 Life cycle environmental analysis ✔ ✔ ✔ ✔ ✔ ✔ ✔ 10/01/11 09/30/12 03/01/11 09/30/12 Completion of LCA analysis

4.2 Life cycle cost analysis ✔ ✔ 10/01/11 03/31/12 05/01/12 09/30/12 Completion of LCC analysis

5.1 Investigate the impact of quality of CO2 gas stream on the chemical conversion process

10/01/12 09/30/13

5.2 Investigate and identify the required down-stream processing to isolate products and the catalyst

10/01/12 09/30/13

5.3 Evaluate the activity of recycled catalyst in flow micro-reactor

10/01/12 09/30/13

6.1 Immobilize the active organocatalysts in the porous MOFs

✔ ✔ ✔ 10/01/12 09/30/13 10/01/12 Synthesis of various MOFs

6.2

Evaluate the activity of chemical conversion using the heterogeneous organocatalytic system in the flow micro-reactor

✔ ✔ ✔

10/01/12 09/30/13 10/01/12 Modification of MOFs with phosphorous ligands

7.1 Evaluate the direct synthesis of cyclic carbonates from olefins in the flow microreactor

✔ ✔ ✔ 10/01/12 09/30/13 10/01/12

Investigation of sequential process for cyclic carbonate from olefins and CO2 with continuous flow reactor

7.2

Investigate the reaction kinetics and mechanisms for the direct synthesis of cyclic carbonate from olefins

✔ ✔ ✔

10/01/12 09/30/13 10/01/12 Reaction kinetic for cyclic carbonate production from olefins and CO2

Bibliography Publication: Kozak, J. A.; Wu, J.; Su, X.; Simeon, F.; Hatton, T. A.; Jamison, T. F., 2013, Bromine-Catalyzed Conversion of CO2 and Epoxides to Cyclic Carbonates under Continuous Flow Conditions, submitted for publication. Wu, J.; Simeon, F.; Hatton, T. A.; Jamsion, T. F., 2013, Mechanism-Guided Design of Flow System for Multicomponent Reactions: Conversion of CO2 and Olefins to Cyclic Carbonates, in preparation. Conference Presentation: Rajvanshi, N.; Arvanitis, E.; Kapur, A.; Hatton, T. A.; Jamison, T. F.; Simeon, F.; Kozak, J. A., 2012, Environmental Life Cycle Assessment of Novel CO2 Capture and Utilization Routes, LCA XII, Tacoma, Washington. Wu, J.; Simeon, F.; Hatton, T. A.; Jamison, T. F. 2013, Mechanism-Guided Design of Flow Systems for Multicomponent Reactions: Conversion of CO2 and Olefins to Cyclic Carbonates, Gordon Conference: Heterocyclic Compounds, Newport, RI. 31

32

Gantt Chart (continued)

Bibliography Publication: Kozak, J. A.; Wu, J.; Su, X.; Simeon, F.; Hatton, T. A.; Jamison, T. F., 2013, Bromine-Catalyzed Conversion of CO2 and Epoxides to Cyclic Carbonates under Continuous Flow Conditions, submitted for publication. Wu, J.; Simeon, F.; Hatton, T. A.; Jamsion, T. F., 2013, Mechanism-Guided Design of Flow System for Multicomponent Reactions: Conversion of CO2 and Olefins to Cyclic Carbonates, in preparation. Conference Presentation: Rajvanshi, N.; Arvanitis, E.; Kapur, A.; Hatton, T. A.; Jamison, T. F.; Simeon, F.; Kozak, J. A., 2012, Environmental Life Cycle Assessment of Novel CO2 Capture and Utilization Routes, LCA XII, Tacoma, Washington. Wu, J.; Simeon, F.; Hatton, T. A.; Jamison, T. F. 2013, Mechanism-Guided Design of Flow Systems for Multicomponent Reactions: Conversion of CO2 and Olefins to Cyclic Carbonates, Gordon Conference: Heterocyclic Compounds, Newport, RI. 33